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Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter

Influence of stimuli from populations of Peromyscus leucopus on maturation of young

The effects of stimuli associated with conspecific laboratory populations on parameters of sexual maturation in Peromyscus leucopus were examined. Beginning at birth, experimental litters were exposed to the constant infusion of urine, feces, and other material from the populations through a metabolism funnel into their cages. As evidenced by age at first vaginal estrus, experimental females matured later than controls. They also had lighter weight reproductive organs. Testis weights were much greater in control than experimental males. These data suggest that stimuli from populations of P. leucopus can inhibit reproductive maturation of conspecifics. In view of the well-documented effects of chemical stimuli on reproductive maturation and function in other rodents, it is suggested that chemical stimuli in the feces, urine, or from other sources mediated the reproductive inhibition observed in this study.

Journal of Mammalogy

The calculation of aquifer chemistry in hot-water geothermal systems

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Journal of Research of the U.S. Geological Survey

Some morphometric properties of experimentally cratered surfaces

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Journal of Research of the U.S. Geological Survey

Sediment accretion rates and sediment composition in Prairie Pothole wetlands under varying land use practices, Montana, United States

Increased sedimentation and nutrient cycle changes in Prairie Pothole Region wetlands associated with agriculture threaten the permanence and ecological functionality of these important resources. To determine the effects of land use on sedimentation and nutrient cycling, soil cores were analyzed for cesium-137 ( 137 Cs), lead-210 ( 210 Pb), and potassium-40 ( 40 K) activities; textural composition; organic and inorganic carbon (C); and total nitrogen (N) from twelve wetlands surrounded by cropland, Conservation Reserve Program (CRP) lands, or native prairie uplands. Separate soil cores from nine of these wetlands were also analyzed for phosphorus (P), nitrate (NO 3 ), and ammonium (NH 4 ) concentrations. Wetlands surrounded by cropland had significantly greater linear sediment accretion rates than wetlands surrounded by CRP or native prairie. Linear sediment accretion rates from wetlands surrounded by cropland were 2.7 and 6 times greater than wetlands surrounded by native prairie when calculated from the initial and peak occurrence of 137 Cs, respectively, and 0.15 cm y−1 (0.06 in yr−1) greater when calculated from 210 Pb. Relative to wetlands surrounded by CRP, linear sediment accretion rates for wetlands surrounded by cropland were 4.4 times greater when calculated from the peak occurrence of 137 Cs. No significant differences existed between the linear sediment accretion rates between wetlands surrounded by native prairie or CRP uplands. Wetlands surrounded by cropland had increased clay, P, NO 3 , and NH 4 , and decreased total C and N concentrations compared to wetlands surrounded by native prairie. Wetlands surrounded by CRP had the lowest P and NO 3 concentrations and had clay, NH 4 , C, and N concentrations between those of cropland and native prairie wetlands. We documented increased linear sediment accretion rates and changes in the textural and chemical properties of sediments in wetlands with cultivated uplands relative to wetlands with native prairie uplands. These findings demonstrate the value of the CRP at protecting wetland catchments to reduce sedimentation.

Montana

Natural trophic variability in a large, oligotrophic, near-pristine lake

Conclusions drawn from stable isotope data can be limited by an incomplete understanding of natural isotopic variability over time and space. We quantified spatial and temporal variability in fish carbon and nitrogen stable isotopes in Lake Hövsgöl, Mongolia, a large, remote, oligotrophic lake with an unusually species-poor fish community. The fish community demonstrated a high degree of trophic level overlap. Variability in δ 13 C was inversely related to littoral-benthic dependence, with pelagic species demonstrating more δ 13 C variability than littoral-benthic species. A mixed effects model suggested that space (sampling location) had a greater impact than time (collection year) on both δ 13 C and δ 15 N variability. The observed variability in Lake Hövsgöl was generally greater than isotopic variability documented in other large, oligotrophic lakes, similar to isotopic shifts attributed to introduced species, and less than isotopic shifts attributed to anthropogenic chemical changes such as eutrophication. This work complements studies on isotopic variability and changes in other lakes around the world.

Journal of Great Lakes Research

Wetland ecosystems studies from a hydrologic perspective

Selected studies from the literature were reviewed to determine the extent of knowledge about the relationship between hydrology and wetland ecosystem studies. Wetland studies of chemical input-output relationships have been the most dependent on hydrologic data of all wetland investigations; yet, very few of these studies have attempted to measure all components of a wetland's water balance. Usually, unmeasured components were calculated as the difference between measured inputs and outputs. Ground water frequently was overlooked. Chemical input-output investigations primarily were concerned with determining the amount of input retained in the wetlands. Few studies also included direct measurement of biogeochemical processes within wetlands of elements that were part of simultaneous input-output investigations. The importance of uncertainties in chemical budgets that are due to uncertainties in hydrologic budgets has been addressed in very few wetland investigations. Although many studies have emphasized the importance of hydrology to wetland ecosystem research, few studies have documented this, so that hydrology remains one of the least understood components of wetland ecosystems.

Journal of the American Water Resources Associatio

Case histories of wild birds killed intentionally with famphur in Georgia and West Virginia

Five incidences of bird mortality in Georgia and West Virginia (USA) involving migratory waterfowl, cranes, raptors, corvids and songbirds were investigated during the first 6 mo of 1988. Gross and histopathologic examinations revealed no evidence of infectious or other diseases. However, severe depression of cholinesterase activity was evident in brains of birds found dead, suggesting gross exposure to an organophosphorus (OP) or carbamate pesticide. All of the gastrointestinal tract contents chemically analyzed contained famphur, an OP insecticide used as a pour-on treatment against lice and grubs on livestock, ranging from 5 to 1,480 ppm (wet weight). Grain scattered at two of the mortality sites contained 4,240 and 8,500 ppm famphur. Gastrointestinal tracts of most of the dead birds contained mainly corn and some wheat. This is the first report to document the use of famphur as an intentional means of killing wildlife thought to be depredating crops.

Journal of Wildlife Diseases

Functional groups in a single pteridosperm species: Variability and circumscription (Pennsylvanian, Nova Scotia, Canada)

Multiple foliar specimens of the Late Pennsylvanian fossil pteridosperm [gymnosperm] Alethopteris zeilleri (Ragot) Wagner were collected from one restricted stratigraphical horizon in the Canadian Sydney Coalfield. Variability of functional-group distribution using FTIR technique was studied in compressions, adaxial versus abaxial cuticles, and in unseparated cuticles as a function of maceration time from 48 to 168??h. The results obtained document spectral variability that could be expected within specimens of one species. For example, CH2/CH3 and Al/ox ratios can differ by as much as 20% of the values. Moreover, the experiments performed confirm that by using a previously established maceration protocol, long maceration periods do not bias FTIR spectra in terms of oxygenation overprinting. The inference that this cuticle is robust, under the given diagenetic level, probably reflects a reassuring degree of chemical fidelity of the Pennsylvanian plant to support Carboniferous chemotaxonomic observations. ?? 2006 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

Evidence from 12-year study links ecosystem changes in the Gulf of Maine with climate change

Investigators at the Bigelow Laboratory for Ocean Sciences (East Boothbay, Maine) and the U.S. Geological Survey collaborated to study ecosystem changes in the Gulf of Maine. As part of the Gulf of Maine North Atlantic Time Series (GNATS), a comprehensive long-term study of hydrographic, biological, optical and chemical properties, multiple cruises have been conducted each year since 2001 by using a portable laboratory aboard different vessels (figure 1) and occasionally a remotely controlled glider (figure 2). Data collected during these cruises, when analyzed within the context of a century of climatological and streamflow data, document changes in temperature, salinity, and coastal ocean productivity that appear to be related to recent increases in precipitation and streamflow. These results are evidence of a link between changing hydrologic conditions on land and changes in coastal ocean productivity.

EcoSystem Indicator Partnership Journal

Groundwater recharge and agricultural contamination

Agriculture has had direct and indirect effects on the rates and compositions of groundwater recharge and aquifer biogeochemistry. Direct effects include dissolution and transport of excess quantities of fertilizers and associated materials and hydrologic alterations related to irrigation and drainage. Some indirect effects include changes in water–rock reactions in soils and aquifers caused by increased concentrations of dissolved oxidants, protons, and major ions. Agricultural activities have directly or indirectly affected the concentrations of a large number of inorganic chemicals in groundwater, for example NO 3 – , N 2 , Cl, SO 4 2– , H + , P, C, K, Mg, Ca, Sr, Ba, Ra, and As, as well as a wide variety of pesticides and other organic compounds. For reactive contaminants like NO 3 – , a combination of chemical, isotopic, and environmental-tracer analytical approaches might be required to resolve changing inputs from subsequent alterations as causes of concentration gradients in groundwater. Groundwater records derived from multi-component hydrostratigraphic data can be used to quantify recharge rates and residence times of water and dissolved contaminants, document past variations in recharging contaminant loads, and identify natural contaminant-remediation processes. These data indicate that many of the world's surficial aquifers contain transient records of changing agricultural contamination from the last half of the 20th century. The transient agricultural groundwater signal has important implications for long-term trends and spatial heterogeneity in discharge.

Hydrogeology Journal

Placing prairie pothole wetlands along spatial and temporal continua to improve integration of wetland function in ecological investigations

We evaluated the efficacy of using chemical characteristics to rank wetland relation to surface and groundwater along a hydrologic continuum ranging from groundwater recharge to groundwater discharge. We used 27 years (1974–2002) of water chemistry data from 15 prairie pothole wetlands and known hydrologic connections of these wetlands to groundwater to evaluate spatial and temporal patterns in chemical characteristics that correspond to the unique ecosystem functions each wetland performed. Due to the mineral content and the low permeability rate of glacial till and soils, salinity of wetland waters increased along a continuum of wetland relation to groundwater recharge, flow-through or discharge. Mean inter-annual specific conductance (a proxy for salinity) increased along this continuum from wetlands that recharge groundwater being fresh to wetlands that receive groundwater discharge being the most saline, and wetlands that both recharge and discharge to groundwater (i.e., groundwater flow-through wetlands) being of intermediate salinity. The primary axis from a principal component analysis revealed that specific conductance (and major ions affecting conductance) explained 71% of the variation in wetland chemistry over the 27 years of this investigation. We found that long-term averages from this axis were useful to identify a wetland’s long-term relation to surface and groundwater. Yearly or seasonal measurements of specific conductance can be less definitive because of highly dynamic inter- and intra-annual climate cycles that affect water volumes and the interaction of groundwater and geologic materials, and thereby influence the chemical composition of wetland waters. The influence of wetland relation to surface and groundwater on water chemistry has application in many scientific disciplines and is especially needed to improve ecological understanding in wetland investigations. We suggest ways that monitoring in situ wetland conditions could be linked with evolving remote sensing technology to improve our ability to better inform decisions affecting wetland sustainability and provide periodic inventories of wetland ecosystem services to document temporal trends in wetland function and how they respond to contemporary land-use change.

North Dakota

Predicting ground-water movement in large mine spoil areas in the Appalachian Plateau

Spoil created by surface mining can accumulate large quantities of ground-water, which can create geotechnical or regulatory problems, as well as flood active mine pits. A current study at a large (4.1 km2), thick, (up to 90 m) spoil body in eastern Kentucky reveals important factors that control the storage and movement of water. Ground-water recharge occurs along the periphery of the spoil body where surface-water drainage is blocked, as well as from infiltration along the spoil-bedrock contact, recharge from adjacent bedrock, and to a minor extent, through macropores at the spoil's surface. Based on an average saturated thickness of 6.4 m for all spoil wells, and assuming an estimated porosity of 20%, approximately 5.2 x 106 m3 of water is stored within the existing 4.1 km2 of reclaimed spoil. A conceptual model of ground-water flow, based on data from monitoring wells, dye-tracing data, discharge from springs and ponds, hydraulic gradients, chemical data, field reconnaissance, and aerial photographs indicate that three distinct but interconnected saturated zones have been established: one in the spoil's interior, and others in the valley fills that surround the main spoil body at lower elevations. Ground-water movement is sluggish in the spoil's interior, but moves quickly through the valley fills. The conceptual model shows that a prediction of ground-water occurrence, movement, and quality can be made for active or abandoned spoil areas if all or some of the following data are available: structural contour of the base of the lowest coal seam being mined, pre-mining topography, documentation of mining methods employed throughout the mine, overburden characteristics, and aerial photographs of mine progression.Spoil created by surface mining can accumulate large quantities of ground-water, which can create geotechnical or regulatory problems, as well as flood active mine pits. A current study at a large (4.1 km2), thick, (up to 90 m) spoil body in eastern Kentucky reveals important factors that control the storage and movement of water. Ground-water recharge occurs along the periphery of the spoil body where surface-water drainage is blocked, as well as from infiltration along the spoil-bedrock contact, recharge from adjacent bedrock, and to a minor extent, through macropores at the spoil's surface. Based on an average saturated thickness of 6.4 m for all spoil wells, and assuming an estimated porosity of 20%, approximately 5.2 ?? 106 m3 of water is stored within the existing 4.1 km2 of reclaimed spoil. A conceptual model of ground-water flow, based on data from monitoring wells, dye-tracing data, discharge from springs and ponds, hydraulic gradients, chemical data, field reconnaissance, and aerial photographs indicate that three distinct but interconnected saturated zones have been established: one in the spoil's interior, and others in the valley fills that surround the main spoil body at lower elevations. Ground-water movement is sluggish in the spoil's interior, but moves quickly through the valley fills. The conceptual model shows that a prediction of ground-water occurrence, movement, and quality can be made for active or abandoned spoil areas if all or some of the following data are available: structural contour of the base of the lowest coal seam being mined, pre-mining topography, documentation of mining methods employed throughout the mine, overburden characteristics, and aerial photographs of mine progression.

International Journal of Coal Geology

Metal prices in the United States through 2010

This report, which updates and revises the U.S. Geological Survey (USGS) (1999) publication, “Metal Prices in the United States Through 1998,” presents an extended price history for a wide range of metals available in a single document. Such information can be useful for the analysis of mineral commodity issues, as well as for other purposes. The chapter for each mineral commodity includes a graph of annual current and constant dollar prices for 1970 through 2010, where available; a list of significant events that affected prices; a brief discussion of the metal and its history; and one or more tables that list current dollar prices. In some cases, the metal prices presented herein are for some alternative form of an element or, instead of a price, a value, such as the value for an import as appraised by the U.S. Customs Service. Also included are the prices for steel, steel scrap, and iron ore—steel because of its importance to the elements used to alloy with it, and steel scrap and iron ore because of their use in steelmaking. A few minor metals, such as calcium, potassium, sodium, strontium, and thorium, for which price histories were insufficient, were excluded. The annual prices given may be averages for the year, yearend prices, or some other price as appropriate for a particular commodity. Certain trade journals have been the source of much of this price information—American Metal Market, ICIS Chemical Business, Engineering and Mining Journal, Industrial Minerals, Metal Bulletin, Mining Journal, Platts Metals Week, Roskill Information Services Ltd. commodity reports, and Ryan’s Notes. Price information also is available in minerals information publications of the USGS (1880–1925, 1996–present) and the U.S. Bureau of Mines (1926–95), such as Mineral Commodity Summaries, Mineral Facts and Problems, Mineral Industry Surveys, and Minerals Yearbook. In addition to prices themselves, these journals and publications contain information relevant to prices, which has been helpful in the preparation of this publication. Prices in this report have been graphed in 1992 constant dollars to show the effects of inflation as measured by the U.S. Bureau of Labor Statistics Consumer Price Index for All Urban Consumers, a widely used measure of overall inflation in the United States. These prices are not tabulated, but a table of the deflators used is given in an appendix. Constant dollar prices can be used to show how prices that producers receive would have less purchasing power.

Scientific Investigations Report

Granitic boulder erosion caused by chaparral wildfire: Implications for cosmogenic radionuclide dating of bedrock surfaces

Rock surface erosion by wildfire is significant and widespread but has not been quantified in southern California or for chaparral ecosystems. Quantifying the surface erosion of bedrock outcrops and boulders is critical for determination of age using cosmogenic radionuclide techniques, as even modest surface erosion removes the accumulation of the cosmogenic radionuclides and causes significant underestimate of age. This study documents the effects on three large granitic boulders following the Esperanza Fire of 2006 in southern California. Spalled rock fragments were quantified by measuring the removed rock volume from each measured boulder. Between 7% and 55% of the total surface area of the boulders spalled in this single fire. The volume of spalled material, when normalized across the entire surface area, represents a mean surface lowering of 0.7–12.3 mm. Spalled material was thicker on the flanks of the boulders, and the height of the fire effects significantly exceeded the height of the vegetation prior to the wildfire. Surface erosion of boulders and bedrock outcrops as a result of wildfire spalling results in fresh surfaces that appear unaffected by chemical weathering. Such surfaces may be preferentially selected by researchers for cosmogenic surface dating because of their fresh appearance, leading to an underestimate of age.

California

Effects of coal storage in air on physical and chemical properties of coal and on gas adsorption

This paper investigates changes in the high-volatile bituminous Lower Block Coal Member from Indiana owing to moisture availability and oxidation in air at ambient pressure and temperature over storage time. Specifically, it investigates changes in chemistry, in surface area, and pore structure, as well as changes in methane and carbon dioxide adsorption capacities. Our results document that the methane adsorption capacity increased by 40%, whereas CO 2 adsorption capacity increased by 18% during a 13-month time period. These changes in adsorption are accompanied by changes in chemistry and surface area of the coal. The observed changes in adsorption capacity indicate that special care must be taken when collecting samples and preserving coals until adsorption characteristics are measured in the laboratory. High-pressure isotherms from partially dried coal samples would likely cause overestimation of gas adsorption capacities, lead to a miscalculation of coal-bed methane prospects, and provide deceptively optimistic prognoses for recovery of coal-bed methane or capture of anthropogenic CO 2 . ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology